The present invention relates to a method of producing a composite material having a high SiO2 content, wherein quartz glass grains are embedded in an SiO2-containing matrix, the method comprising the following steps: preparing a suspension from a particle mixture consisting of finely divided SiO2 powder having at least two different particle fractions and of said quartz glass grains, forming the suspension into a green compact, and sintering the green compact.
Furthermore, the present invention relates to a composite material comprising an SiO2-containing matrix in which glass grains are embedded.
Furthermore, the present invention relates to a permanent mold made of the composite material according to the invention.
Structural members consisting of a composite material having a high SiO2 content of at least 99% by wt. are characterized by a small coefficient of expansion and by high chemical resistance. Such structural members are e.g. used in metallurgy, e.g. in the form of crucibles for melting metals, nozzles, protective tubes or pouring channels.
A composite material according to the above-mentioned type and a method for producing a refractory sintered article of silica glass is known from DE 693 06 169 (T2). This document describes a method in which two SiO2 powders with different particle sizes are used as the starting materials having a binder phase for a further SiO2-containing component in the form of coarse SiO2 grains with a grain size between 40 xcexcm and 1000 xcexcm. The two more fine-grained SiO2 powders are present, on the one hand, as quartz dust which is formed from substantially spherical particles, or as fine-grained SiO2 particles of a particle size below 40 xcexcm. These components are premixed in a dry-milling process, and a slip is then made therefrom under addition of a stabilizer. The weight percent of the individual components are, in the order of their above indication, 54% (coarse SiO2 grains), 33% (fine-grained SiO2 particles) and 13% (quartz dust). The slip is degassed under vacuum and cast into a plaster mold. The green compact produced thereby is dried and sintered in a furnace at 1050xc2x0 C. to obtain the composite structural member. Coarse quartz glass grains which are embedded in a relatively continuous matrix of fine particles and of spherical particles of quartz dust are typical of the microstructure of the structural member. The structural member has an open porosity of 13%, and its density is at 1.91 g/cm3. The crystallographic analysis shows a cristobalite content of less than 2%.
On account of its open, i.e. continuous, porosity, the known composite material cannot be used in unlimited form for structural members in the case of which density or high purity are of importance. Metallic melts can penetrate into the wall of the structural member through the pores and result in leakage. In principle, a higher density and a lower porosity could be achieved through a higher sintering temperature or a longer sintering period, but an increased cristobalite formation would have to be accepted. The formation of cristobalite is caused by impurities of the starting components or by possible additives such as stabilizers and sintering adjuvants, and rapidly progresses at elevated temperatures. This, however, would entail a reduced resistance to temperature changes and a lower strength of the composite material.
It is therefore the object of the present invention to indicate a method which permits an inexpensive production of a composite material having a high SiO2 content of at least 99% by wt. which is characterized by a high resistance to temperature changes together with a high density, and to provide a composite material which is suited for applications where temperature resistance, density and high purity are of importance, and to indicate a suitable use thereof.
As for the method, this object starting from the above-mentioned method is achieved according to the invention in that the matrix has an SiO2 content of at least 99% by wt. and is formed from at least a first and a second particle fraction, each of said particle fractions being present as granules of nanoscale, amorphous, synthetically produced SiO2 primary particles having a mean primary particle size of less than 100 nm.
For the preparation of the composite material, exclusive use is made of amorphous starting substances in the method according to the invention and also in the above-described known method, so that in the composite material the (vitreous) quartz glass grains are embedded in a matrix (binding phase) which also consists essentially of quartz glass. Due to the fact that the two essential components of the composite material, namely xe2x80x9cmatrixxe2x80x9d and xe2x80x9cquartz glass grainsxe2x80x9d, consist of amorphous SiO2, stresses caused by different coefficients of expansion are avoided. The matrix is formed from at least two different particle fractions which, in contrast to the known method, are each formed as granules of nanoscale, amorphous, synthetically produced SiO2 primary particles.
The quartz glass grains serve as a filler. They are devoid of any open porosity and restrict shrinkage of the green compact during sintering. A closed porosity of the quartz glass grains is not detrimental to the method according to the invention and may be necessary, for instance for setting the desired opacity of the material.
The porosity of the composite material is essentially defined by the matrix. In the method according to the invention, the matrix is substantially formed by sinter-active components, as will be explained in more detail in the following. The use of at least two different particle fractions for forming the matrix permits a higher packing density in the green compact together with an optimization of density and strength of the composite material.
Said optimized condition is brought about by the particle fractions differing from one another, either in the size of the granules, their density or with respect to their sinterability; density and sinterability of the respective particle fraction are here substantially set by thermal pretreatment.
Due to the fact that at least the first particle fraction and the second particle fraction consist of granules formed from nanoscale, amorphous SiO2 primary particles having a mean primary particle size of less than 100 nm, compaction and consolidation that are of advantage to the later sintering process are already observed in the green compact stage. This is due to a certain solubility and movability of the individual SiO2 primary particles in the suspension, which contributes to the so-called xe2x80x9cneck formationxe2x80x9d between neighboring granules in the green compact. During drying of the SiO2-enriched liquid phase in the area of the xe2x80x9cnecksxe2x80x9d, said necks consolidate, resulting in a firm connection of the individual granular particles and in a compaction and consolidation of the green compact which facilitate the subsequent sintering process and thus yield a relatively high density of the composite material, i.e. already at a low sintering temperature. The solubility of individual primary particles and of the granules formed therefrom in the suspension is the more pronounced the greater the specific surface of the granule is. These effects based on the nanoscale amorphous SiO2 primary particles have a stabilizing influence on both the green compact and the composite material. Therefore, the method according to the invention makes it possible to form the green compact without the help of binders and stabilizers and permits a sintering of the composite material without the addition of sintering adjuvants. Thus, the impurities in the composite material that accompany the use of such an additive are avoided.
Hence, due to their high sintering activity, the nanoscale, amorphous SiO2 primary particles contribute to a high density, mechanical strength and purity of the composite material.
This effect of the amorphous SiO2 primary particles which is conducive to mechanical strength and density is intensified in that the method according to the invention allows a sintering of the green compact at a relatively high sintering temperature without start of a cristobalite formation impairing the strength of the composite material. This is due to the fact that the SiO2 primary particles are produced synthetically, and the granules formed therefrom have correspondingly low contents of impurities. A low content of impurities, in turn, permits sintering at a high temperature without an ensuing devitrification, resulting in a composite material of a high density and strength. The purity of the granules is even enhanced by the fact that they can be produced without organic binders as are otherwise used in the preparation of granules. This is made possible by the above-described compaction and consolidation effect of the primary particles which is also observed in the production of granules.
Such primary particles are e.g. obtained by flame hydrolysis or oxidation of silicon compounds by hydrolysis according to the so-called sol-gel method or in a liquid. The finely divided primary particles obtained in this way are compacted by means of granulation methods, with granules being formed in the sense of the present invention by the agglomeration of the finely divided primary particles. Thus, the granules are a multiple of the size of a primary particle. The size of the primary particles is in the nanometer range, whereas that of the granules is normally within the micrometer range or above. It is possible to achieve impurity contents of Li, Na, K, Mg, Ca, Fe, Cu, Cr, Mn, Ti and Zr within the granules that amount to a total of less than 1 ppm by wt. Dopants that have intentionally been added are no impurities in this sense.
SiO2 primary particles produced by flame hydrolysis of a silicon-containing starting compound have turned out to be particularly suited. Such SiO2 primary particles are characterized by a particularly high purity and sintering activity so that their granulation can be carried out by means of known granulation methods without the addition of external binders because a binding effect at the contact points of individual primary particles is achieved by internal material through the above-explained sol-gel binding.
It has been found to be advantageous when use is made of a first particle fraction that has a specific BET surface area of at least 40 m2/g. Such a relatively large BET surface area guarantees a high sintering activity of said granules (hereinafter also designated as xe2x80x9cfine granulesxe2x80x9d), the mean particle size of which is typically below about 160 xcexcm. The surface of the fine granules is composed of outer and inner surface, the latter being substantially defined by continuous pore channels which after the sintering process are present as closed pores and give the composite material an opaque appearance.
It has been found to be advantageous when the second particle fraction has a smaller specific BET surface area than the first particle fraction. Due to the smaller BET surface area, the second particle fraction shows reduced shrinkage during drying and sintering, so that dimensional stability and accuracy of the green compact are influenced by the addition of said particle fraction. The second particle fraction preferably shows a specific BET surface area of 35 m2/g or less. The second particle fraction comprises preferably coarser particles than the first particle fraction and can thus be consolidated by thermal treatment without any major problems. The mean particle size is normally above 200 xcexcm (said second particle fraction will also be designated as xe2x80x9ccoarse granulesxe2x80x9d in the following).
The first and second particle fractions are preferably obtained by granulation of nanoscale amorphous SiO2 particles and subsequent thermal consolidation of the granules produced. The thermal consolidation of the granules produced in this way is carried out at a temperature ranging from 900xc2x0 C. to 1450xc2x0 C., with the proviso that the temperature during sintering of the first particle fraction is lower than during sintering of the second particle fraction.
The quartz glass grains have preferably a specific BET surface area of 1 m2/g or less. These are amorphous particles of synthetic SiO2 or of natural raw material. The grains have either no continuous pores or have a small amount of continuous pores and do not contribute to any shrinkage of the green compact during drying and sintering. They serve mainly as a filler, but can also be selected with respect to a special effect on the physical or chemical properties of the composite material. For instance, for increasing the infrared transparency of the composite material, transparent grains are rather preferred, whereas bubble-containing grains have the opposite effect and give the composite material an opaque appearance. The particle size has no essential influence on the function of the quartz glass grains as xe2x80x9cfillersxe2x80x9d, so that suitable grain sizes may range from 0.1 to 4 mm.
It has been found to be of advantage when use is made of a particle mixture that additionally comprises SiO2 primary particles that are not agglomerated or only agglomerated to a slight degree and have a specific BET surface area of at least 40 m2/g. The SiO2 primary particles are substantially present in a non-agglomerated form. They have a binder-like effect in the green compact and enhance the density and mechanical strength of said compact by promoting neck formation during drying. Moreover, the addition of the primary particles has a positive effect on the sintering activity. The non-agglomerated SiO2 primary particles are added to the particle mixture in addition to the above-described particle fractions and the quartz glass grains, and they are preferably added, as will be described in the following, as a suspension.
The composite material is preferably produced by the so-called slip casting method. A suspension is here produced from a liquid and at least a part of the SiO2-containing starting components. The particle mixture can be homogenized in a particularly easy way if the SiO2 primary particles are provided in a suspension, also in a slightly agglomerated form. The remaining starting components are then also introduced into the suspension and homogenized therein.
As for the composite material, the above-indicated object, starting from the composite material of the above-mentioned type, is achieved according to the invention in that the matrix comprises an SiO2 content of at least 99% by wt.
The composite material according to the invention is characterized by a matrix having a high SiO2 content of at least 99% by wt. The high SiO2 content permits the production of the composite material by sintering a green compact at a relatively high sintering temperature or for a long sintering period without a pronounced cristobalite formation. A cristobalite formation would impair the resistance to temperature changes and the strength of the composite material. A high density and thus a small open porosity can however be set by choosing a high sintering temperature and/or long sintering duration.
The small impurity content of the matrix thus permits a sintering operation at a temperature which is high in comparison with the known method, and thus the production of a composite material having a high density, high resistance to temperature changes and high strength.
The density and mechanical strength of the composite material are substantially determined by the matrix. As has already been described with respect to the method according to the invention, the matrix is substantially formed from agglomerates of nanoscale, synthetically produced, amorphous SiO2 primary particles which contribute to a high density and mechanical strength of the composite material solely by reason of their high sintering activity. Moreover, the degree of purity of the matrix is additionally enhanced because it can be produced without the addition of external, in particular alkali-containing, binders.
Moreover, the composite material according to the invention is characterized by a matrix which consists entirely of an amorphous phase. As a result, mechanical stresses between the matrix and the quartz glass grains embedded therein are avoided because matrix and quartz glass grains have the same coefficient of expansion.
It has been found that a composite material produced according to the method of the invention is particularly suited as a starting material for producing a permanent mold for melting solar silicon. Impermeability of the material to the silicon melt, and thus a high density, are imperative for this intended use; in addition, mechanical strength and temperature-change resistance of the permanent mold are required, said characteristics being obtained when the permanent mold is produced from a composite material as obtained according to the method of the invention.